CN104918686A - Filtration membranes with nanoscale patterns - Google Patents

Abstract

A membrane for fluid transfer includes a base membrane and a pattern, that covers a working area of a surface thereof, formed of a compatible material. The pattern has periodicity and/or amplitude that do not exceed 1 micrometer. A method of filtering a component from a solution includes passing the solution comprising the component through a membrane that includes a base membrane. The base membrane and a pattern that covers a working area of a surface thereof are formed of materials compatible with the solution. The pattern has periodicity and/or amplitude that do not exceed 1 micrometer, and reduces mass transfer of surface-accumulative soluble and/or suspended species and particulates from the solution to the membrane while the solution is passed through the membrane. A method of producing a membrane for fluid transfer includes forming a nanoscale pattern over a working area of a polymer membrane.

Description

There is the filter membrane of nano-scale patterns

Background technology

Polymer film has obtained critical role and for applying widely in pressure-actuated isolation technics.Because they control the infiltration of chemical substance by material, so they play an important role in various technical matters.Although have these all advantages, but the continued operation of these films is subject in film surface, hole or the pollution at hole wall place (fouling) phenomenon (such as, the deposition of left particle, colloid, macromolecule, salt etc.) obstruction, cause the reduction [1-3] from initial rate on infiltration/flux.

Pollution starts to be the form of " concentration polarization ", and wherein, the condensate accumulating of filtering composition is near film surface.This can increase the osmotic pressure,effective of cross-film, causes high molecular gel layer, causes the sedimentation of indissoluble state salt, or starts the deposition [4,5] of particle cake at film near surface.In its earliest stages, pollution is reversible, and this is because initial infiltration/flux can be reduced by stopping filtering or perform light flushing (such as, applying back pressure) usually.Because the concentration of filtering thing increases, therefore film becomes more adhesively contaminated, causes the flux being more difficult to reverse to decline (it requires that more complicated cleaning is with reversion), and in fact can become irreversible.When flux declines generation, along with cake/pollution layer applies the other resistance being called " resistance of filter cake ", water resistance increases [6,7].In order to contaminated solution, dissimilar pretreatment and cleaning program are developed by particular process industry and are used.Usually, due to irreversible composition as mentioned before, therefore flux decline increases energy consumption (such as, in order to keep directed fluid flux) and limits the service life [1,2] of film.Therefore, in the field of membrane technology, a lot of work has been adopted to carry out decreasing pollution.

With the membrane separation process mainly superficial phenomenon [3,8] polluted.Large quantifier elimination is carried out, with decreasing pollution in the surface of Modified Membrane.In these work, many objects are to change surface energy, and such as, increase the hydrophily of film, this is the absorption [3] contributed to because pollutant is under a cloud on hydrophobic surface.Utilize the absorption of kinds of surface activating agent and polymer to increase the hydrophily [9-11] of film.In addition, a large amount of work [12-14] has been carried out about by the polymer-coated based on polyvinyl alcohol (PVA) and polyethylene glycol (PEG) on the surface to film.Based on the common technology [15-17] that the polymer of PEG and the surface grafting of hydroxyethyl methacrylate are modified membrane surfaces.In addition, CO is used ₂, N ₂, O ₂the hydrophily [18-21] increasing film surface has been used to the multiple plasma treatment of UV.But the extensive use of all these techniques is restricted, this is because much technique completes under unsafe conditions.In addition, grafting and coating are tended to temporary transient, and the most of technology in these technology carries out being expensive [3,21] at industrial scale.

Summary of the invention

The invention solves multiple aforementioned challenges, which provide the film for fluid conveying, comprise the pattern that formed by nanolithographic and have periodically and the feature of amplitude, this characteristics play is to resistant to pollution effect.Film of the present invention can be filter membrane.Filter membrane comprises the film being suitable for nanofiltration, ultrafiltration, micro-filtration and counter-infiltration.

Present invention also offers a kind of film, this film comprises the part of protruding part or depression on the surface of the film to form shape, and wherein, the degree of depth of the paddy between these shapes or amplitude are between 50nm and 500nm.In some embodiments, these shapes are arranged to the periodicity that has between 10nm and 1500nm or between 400nm and 1000nm.In other embodiments, these shapes are arranged to have the periodicity of about 834nm.

In some embodiments of film, amplitude is between 10nm and 300nm.In other embodiments, amplitude is about 200nm.In some embodiments, the space between shape or paddy have the width between 200nm and 800nm or the width between 300nm and 600nm.In other embodiments, paddy is the width of about 400nm.

In some embodiments of film, film has the molecular cut off (MWCO) between 0.1kDa and 1000kDa.In other embodiments, film comprises polyether sulfone.

The invention provides the method using film described herein from filtering flow component.Fluid can be liquid or gas.In some embodiments, liquid is polar solvent.

In some embodiments, the invention provides a kind of method from aqueous solution filter component, the method comprises the aqueous solution making to comprise described component and passes film described herein.In some embodiments, described component has the molecular weight between 0.1kDa and 1000kDa.In other embodiments, filter and at room temperature carry out.Room temperature can be about 21 DEG C.

In some embodiments of filter method, filter and carry out under the pressure of 6psi and 51psi.In other embodiments, filter and carry out under subcritical flux.In a specific embodiment, when component to have the average grain diameter of 250nm by diameter, critical flux is greater than 40Lm ^-2h ^-1or at 40Lm ^-2h ^-1and 60Lm ^-2h ^-1between.In some embodiments, under the above parameters, film has the paddy degree of depth of about 400nm.

In a specific embodiment, when component has the average grain diameter of 500nm by diameter calculator, critical flux is greater than 60Lm ^-2h ^-1or at 60Lm ^-2h ^-1and 90Lm ^-2h ^-1between.In some embodiments, under the above parameters, film has the paddy degree of depth of about 400nm.

Present invention also offers film-forming method described herein, comprise nanoimprint lithography (NIL).NIL can be heat embossing NIL or stepping-flash of light NIL.

In some embodiments of film-forming method described herein, heat embossing NIL comprises: provide film; Under the pressure of about 3MPa to 7MPa, in rigid die, film is pressurizeed; Being heated to by film can higher or lower than the temperature of the glass transition temperature of film; Film is cooled to the temperature of the glass transition temperature lower than film; And film is separated with mould; Prepare film described herein thus.

In another embodiment of the method for preparation film described herein, heat embossing NIL comprises: provide film; Under the pressure of about 3MPa to 7MPa, in rigid die, film is pressurizeed; Film is heated to the temperature between 100 DEG C and 150 DEG C; Film is cooled to the temperature of the glass transition temperature lower than film; And film is separated with mould; Prepare film described herein thus.

In some embodiments of the method for preparation film described herein, rigid die is made up of silicon, polymer, metal, glass, pottery, composite or its combination.In some embodiments, pressurization steps is carried out under the pressure of about 4MPa.In other embodiments, during heating steps, film is heated to the temperature of about 120 DEG C.In some embodiments, heating and pressurization steps carry out about 180 seconds, and in other embodiments, carry out the shorter time for high flux heating and pressurization steps.In other embodiments, before film is separated with mould, film is cooled to the temperature of about 40 DEG C.

In certain embodiments, described and film used is milipore filter in the above-mentioned methods.

In one embodiment, film for fluid conveying comprises: the basement membrane with first surface and the second surface relative with first surface, with the pattern formed by the material compatible with basement membrane, the working region of this pattern covers first surface, pattern formation has size and is no more than the periodicity of 1 micron and the feature of amplitude.

In one embodiment, from solution, the method for filter component comprises: make to comprise the solution of component through film.Film comprises the basement membrane with first surface and the second surface relative with first surface.Basement membrane comprises the material compatible with this solution and comprises the pattern of the material compatible with solution with basement membrane, and it covers the working region of first surface.Pattern formation has size and is no more than the periodicity of 1 micron and the feature of amplitude.The material that is solvable and/or that suspend that pattern decreases that surface gathers and the mass transfer of particle from solution to film, solution is by film simultaneously, and the solvable and/or suspended material that this and surface are gathered and particle are from solution to not having the mass transfer of figuratum basement membrane contrary.

In one embodiment, the method for the preparation of the film of fluid conveying comprises: on the working region of polymer film, forms nano-scale patterns.

Accompanying drawing explanation

Figure 1A illustrates landform AFM (AFM) image of original membrane.

Figure 1B illustrates the landform afm image of the patterned film according to embodiment.

Fig. 1 C illustrates cross section FE-SEM (field emission scanning electron microscope) image of the patterned film of Figure 1B.

Fig. 1 D illustrates the cross section FE-SEM image of the original membrane of Figure 1A.

Fig. 1 E is the Line Chart of three profiles of the original membrane that Figure 1A is shown.

Fig. 1 F is the Line Chart of three profiles of the patterned film that Figure 1B is shown.

Fig. 2 is the schematic diagram of the experimental provision for evaluating filter membrane according to embodiment.

Fig. 3 illustrates the Line Chart for original membrane and the patterned film relation between the transmembrane pressure applied and flux according to embodiment, is plotted as flux to transmembrane pressure.

Fig. 4 illustrates according to the stain resistance measured under each pressure drawn for original membrane and patterned film of embodiment the Line Chart of transmembrane pressure.

Fig. 5 A be illustrate according to embodiment utilize the colloidal suspension liquid of patterned film with the Line Chart of the experimental data of time correlation.

Fig. 5 B be illustrate according to embodiment utilize the colloidal suspension liquid of original membrane with the Line Chart of the experimental data of time correlation.

Fig. 6 A is the schematic diagram in the NIL-patterned film direction illustrated according to embodiment.

Fig. 6 B illustrates the schematic diagram selected for nine parts of the NIL-patterned film of sem analysis, and patterning on the direction illustrated in fig. 6, and arrow instruction is from the footpath flow path direction of center injection.

Fig. 7 A illustrates the SEM image of nine parts of the NIL-patterned film schematically showing pollution in fig. 6b.

Fig. 7 B illustrates the SEM image of nine parts of (original) film of the non-patterned of pollution.

Fig. 8 A illustrates the productivity ratio of non-NIL-patterned film (original), and wherein, the data illustrated in order are for different measurement scheme.

Fig. 8 B illustrates the productivity ratio of NIL-patterned film (vertical axis), and wherein, the data illustrated in order are for different measurement scheme.

Fig. 9 illustrates according to the flux for NIL-patterned film and non-NIL patterned film of embodiment filtration step.Each data point is the mean value of the measured value that three films adopt, and each error line represents the standard deviation of measured value.

Figure 10 A illustrates the SEM image of the BSA deposition in the first test on the surface of non-NIL patterned film (original).

Figure 10 B illustrates the SEM image of the BSA deposition in the second test on the surface of non-NIL patterned film (original).

Figure 10 C illustrates the SEM image of the BSA deposition in the first test on the surface of NIL patterned film according to embodiment.

Figure 10 D illustrates the SEM image of the BSA deposition in the second test on the surface of NIL patterned film according to embodiment.

Figure 11 A is illustrated schematically in the impressing mould relative to basement membrane location in embodiment.

Figure 11 B is illustrated schematically in the patterning filter membrane in embodiment.

Figure 12 is illustrated schematically in the filter membrane formed by the pattern adding basement membrane in embodiment.

Detailed description of the invention

There is provided herein the film for fluid conveying, it comprises: the basement membrane with first surface and the second surface relative with first surface, with the pattern be made up of the material identical with basement membrane or the material compatible with basement membrane, the working region of this pattern covers first surface.Pattern formation has size and is no more than the periodicity of 2 microns and the feature of amplitude.Additionally provide the method for the preparation of this film herein, and for performing nanolithographic to form the equipment of pattern on basement membrane.

Although hereafter described in conjunction with particular implementation and step and disclosed the present invention, but it is not intended to limit the invention to those detailed description of the invention.Otherwise the present invention is intended to cover all fall alternative embodiment within the spirit and scope of the present invention and modification like this.

For the ease of understanding the present invention, hereafter define a large amount of terms.The term that the present invention defines has usual the understood implication of those skilled in the art.The such as term of " " and " being somebody's turn to do " is not used in and only refers to single entity, but comprises the general class that may be used for the specific embodiment illustrated.Term used herein is used for describing detailed description of the invention of the present invention, but their use does not define the present invention.

Term " about " or " approximately " typically refer in 20% of set-point or scope, more preferably in 10% of set-point or scope, more preferably in 5% of set-point or scope.

As used herein, " film " is the barrier separated by two kinds of liquid, and this barrier allows matter selective transmission between the fluids." fluid " can be liquid or gas.

In one embodiment, the aqueous solution is transmitted through film of the present invention, this require this film can make the aqueous solution through.

As used herein, term " flux " was used to refer to and flows through the solution of given diaphragm area or the volume of fluid during preset time.

As used herein, term " critical flux " is used to refer to the permeation flux of membranous system, lower than this permeation flux, does not pollute.Ideally, for clean system, the water flux of film is proportional with the transmembrane pressure (TMP) applied.When flux exceedes its critical value, irreversible deposition and/or pollution start, and flux starts to depart from the linear relationship with TMP.According to the concept of critical flux, when film runs under the pressure of the relevant pressure lower than critical flux, it is restricted to and operates in " subcritical flux " district.Subsequently, when film runs under the pressure higher than critical flux pressure, it operates in " overcritical flux " district.In theory, when film operates in subcritical flux zone, particle-film repulsive force and/or diffuse in reverse direction are subsequently higher than osmotic resistance.At this region place, membrane flux remains unchanged in time.

As used herein, nanoscale refers to that the size of object is less than 2000nm and is greater than 1nm.

The invention provides the preparation and application of patterned film and these films.In some embodiments, film used is filter membrane.

In embodiment more specifically, film is ultrafiltration (UF) film.As used herein, milipore filter is restricted to the film of the molecular cut off (MWCO) had between 1kDa and 1000kDa.As used herein, MWCO refers to the molecular weight of the component that 90% film retains.In one embodiment, milipore filter also has in about 2.5nm and the effective aperture about between 120nm.

In some embodiments, film is nanofiltration membrane.Nanofiltration membrane contains the hole of nano-scale.In one embodiment, nanofiltration membrane filtering can be of a size of the solute of 1nm to 10nm.

In some embodiments, film is microfiltration membranes.Microfiltration membranes has the effective aperture between 45nm and 2500nm.

The invention is not restricted to specific membrane material and can comprise: the film being applicable to micro-filtration, as polypropylene, poly-(vinylidene), poly-(tetrafluoroethene); Be applicable to the film of ultrafiltration, such as, as polysulfones, polyether sulfone; Be applicable to the film of nanofiltration, such as, polyamide; And be suitable for the film of counter-infiltration, and such as, polyamide; And combination.

The type of the film for ultrafiltration of the present invention comprises following material: as polyether sulfone, polyacrylonitrile, polyvinylidene, regenerated cellulose, cellulose acetate, polysulfones, polypropylene, polyether sulphone, Kynoar, polyvinyl chloride, polyketone, polyether-ketone, polytetrafluoroethylene (PTFE), polyimides and/or polyamide and combination thereof.

The type of the film for nanofiltration of the present invention comprises following material: as cellulose acetate, polypiperazine-amide, polyamide, polyethylene, polypropylene, polysulfones, polyether sulfone, polytetrafluoroethylene (PTFE), polyvinylidene fluoride, polyimides and/or polyacrylonitrile and combination thereof.

The type of the film for micro-filtration of the present invention comprises following material: as nylon, mixed cellulose ester, regenerated cellulose, cellulose acetate, polycarbonate, polytetrafluoroethylene (PTFE), polypropylene, polystyrene, polyvinyl chloride, polysulfones, polyether sulfone and/or polyethylene and combination thereof.

Type for reverse osmosis membrane of the present invention comprises following material: as cellulosic acetate, polypiperazine-amide and polyamide.Embodiment herein can comprise in following material one or more: poly-(methyl methacrylate), polystyrene, Merlon, polyimides, epoxy resin, cyclic olefine copolymer, cyclic olefin polymer, acrylate or methacrylate polymers, PETG, poly-phenylethylene, polyether-ether-ketone, poly-(N-VCz), acrylonitritrile-styrene resin, PEI, poly-(phenylene vinylidene), polysulfones, SPSF, the copolymer of styrene and acrylonitrile, poly-(tetrafluoroethene), poly-(Ethylene-Propylene-Diene), poly-(aryiene oxide), Merlon, cellulose acetate, containing the polymer of piperazine, polyelectrolyte, containing cinnamic copolymer, acrylonitritrile-styrene resin, SB, styrene-ethylene base Benzyl halides composition copolymer, cellulosic polymer, acetylbutyrylcellulose, cellulose propionate, ethyl cellulose, methylcellulose, celluloid, polyamide, polyimides, aromatic polyamide, aryl polyimides, polyethers, poly-(aryiene oxide), poly-(phenylene oxide), poly-(xylene oxygen compound), poly-(esteramides vulcabond), polyurethane, polyester (comprising polyarylate), poly-(alkyl methacrylate), poly-(acrylate), poly-(terephthalic acid (TPA) benzene diester), polysulfide, poly-(ethene), poly-(propylene), poly-(butene-1), poly-(4-methylpentene-1), polyvinyl, poly-(vinyl chloride), poly-(PVF), poly-(vinylidene chloride), poly-(vinylidene fluoride), poly-(vinyl alcohol), poly-(vinyl esters), poly-(vinyl acetate), poly-(vinylpropionate), poly-(vinylpyridine), PVP, poly-(vinyl ethers), poly-(vinyl ketone), poly-(hexenal), poly-(vinyl formal), poly-(polyvinyl butyral), poly-(vinylamide), poly-(urethanes), poly-(vinyl urea), poly-(vinyl phosphate), poly-(vinyl sulfate), polyallyl esters, poly-(benzene azoles benzimidazole) (ploy (benzobenzimidazole)), polyhydrazide, polyoxadiazoles, polytriazoles, poly-(benzimidazole), polycarbodiimide, poly-phosphine piperazine and combination thereof.

In other embodiments, film is selected from glassy polymers, dimethyl silicone polymer and its combination.

The patterning of film can use any method as known in the art to perform.In some embodiments, film is patterned by nanolithographic.Nanolithographic creates nanoscale shape on the surface of the film.These shapes can be formed by generating the part of protruding part or depression on film.These shapes can comprise crestal line, and these crestal lines form a series of jut, parallel lines, intersecting lens, concentric line, spheroid and/or other shapes.It is one or more that jut can comprise in hills, bar, mountain peak, pin, pin and/or knob.Advantageously, the size (periodically and/or amplitude) that shape has is less than 2 microns and little of 10nm.Have been found that compared with the film of prior art, the shape of this size suppresses to pollute unexpected degree.

In some embodiments, the film with the pattern of parallel crestal line of the present invention also comprises the other crestal line crossing with parallel crestal line.In some embodiments, described other crestal line is parallel to each other.In some embodiments, described other crestal line is approximately perpendicular to described original parallel crestal line.In some embodiments, described other crestal line is crossing with described parallel crestal line with the angle between 0.01 ° and 90 °.

In some embodiments, basement membrane manufactures in the mode of applicable commercial use, and pattern is made up of the material compatible with basement membrane, and this pattern is added to basement membrane.

In some embodiments, film for fluid conveying is formed by nanolithographic pattern at least one surface, wherein compared with the not figuratum basement membrane of tool, the material that is solvable and/or that suspend that film has that surface gathers and the mass transfer that particle reduces from fluid at least 10% of film surface, fluid is transmitted through film simultaneously.In the particular implementation of these embodiments, the mass transfer of the material that is solvable and/or that suspend that surface is gathered and the minimizing of particle is at least to reduce 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or 100%.

In some embodiments, film for fluid conveying is formed by nanolithographic pattern at least one surface, wherein, with do not have compared with figuratum basement membrane, for any mixture of fluid and/or fluid and solute and/or fluid and particle, the critical flux of the weak form of film has the growth of at least 5%, and has and be transmitted through film compared with the fluid of high permeability.

According to a detailed description of the invention, film is provided with the pattern of series of parallel crestal line or jut.When watching film from the side, each formation mountain peak of these crestal lines or jut, the space between these crestal lines forms paddy.In some embodiments, at the peak-to-peak average distance in each mountain (be also defined as cycle or periodically) between 10nm and 2000nm.In other embodiments, be 10nm, 20nm, 30nm, 50nm, 75nm, 100nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm, 500nm, 550nm, 600nm, 650nm, 700nm, 750nm, 800nm, 850nm, 900nm, 950nm, 1000nm, 1050nm, 1100nm, 1150nm, 1200nm, 1250nm, 1300nm, 1350nm, 1400nm, 1500nm or 2000nm at the peak-to-peak average distance in each mountain.In other embodiments, periodically between 600nm and 800nm.In one embodiment, be periodically on average about 834nm.

As described, when viewed from the side, paddy width herein refers on the film at the average height place of film between 2 mean transverse distance.In some embodiments, average paddy width is between 10nm and 800nm.In other embodiments, average paddy width is 10nm, 50nm, 100nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm, 500nm, 550nm, 600nm, 650nm, 700nm, 750nm or 800nm.

In some embodiments, the degree of depth (being also defined as amplitude) of paddy is between 10nm and 600nm.In other embodiments, the mean amplitude of tide of paddy is 10nm, 20nm, 30nm, 50nm, 100nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm, 500nm, 550nm or 600nm.

The pattern of different size can be used for filtering the particle of different size.In some embodiments, the average paddy width of film and/or amplitude are less than average particle size particle size to be filtered.In some embodiments, average paddy width and/or amplitude are 99% of average particle size particle size to be filtered.In other embodiments, average paddy width and/or amplitude are 120%, 110%, 100%, 95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55% or 50% of average particle size particle size to be filtered.

The theory relation of darcy (Darcy) law utilizes the film surface area increased to predict higher volume flow:

$q=\frac{\mathrm{\Δp}\·A}{\mathrm{\μ}\·R}$

Wherein q is volume flow, Δ p is institute's applied pressure, μ is viscosity, R is membrane resistance and A is the surface area of film.

Film of the present invention may be used for the pretreatment of process water and the post processing of ultra-pure water, and can filter component, such as high molecular weight material, colloidal materials, protein and virus.

Present invention also offers and use patterned film described herein to filter the method for fluid.Filtration can be undertaken by film by making fluid.In some embodiments, fluid is liquid, as polar solvent or non-polar solven.In embodiments, polar solvent can be one or more in water, carrene, oxolane, ethyl acetate, acetone, dimethyl formamide, acetonitrile, methyl-sulfoxide, propene carbonate, formic acid, n-butanol, isopropyl alcohol, normal propyl alcohol, ethanol, methyl alcohol and acetic acid.In other embodiments, non-polar solven can be one or more in pentane, pentamethylene, hexane, cyclohexane, benzene, toluene, Isosorbide-5-Nitrae-dioxane, chloroform and diethyl ether.In another embodiment, fluid is gas.

Filter as described herein can be used for removing particle from solvent.Particle can have various sizes.In some embodiments, between particle average out to 10nm and 1510nm.In other embodiments, diameter average out to 10nm, 20nm, 30nm, 50nm, 75nm, 100nm, 125nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm, 500nm, 550nm, 600nm, 650nm, 700nm, 750nm, 800nm, 850nm, 900nm, 950nm, 1000nm, 1050nm, 1100nm, 1150nm, 1200nm, 1250nm, 1300nm, 1350nm, 1400nm, 1450nm, 1500nm or 1510nm of particle.In some embodiments, the quality of particle is between 1kDa and 1000kDa.In other embodiments, the quality of particle is 0.1kDa, 1kDa, 50kDa, 100kDa, 150kDa, 200kDa, 250kDa, 300kDa, 350kDa, 400kDa, 450kDa, 500kDa, 550kDa, 600kDa, 650kDa, 700kDa, 750kDa, 800kDa, 850kDa, 900kDa, 950kDa or 1000kDa.According to filter method described herein, filtration can be carried out at any temperature.In some embodiments, filter and carry out under room temperature (such as, between 18 DEG C and 25 DEG C).In other embodiments, filter and carry out between 1 DEG C and 50 DEG C.In other embodiments, filter and carry out at 1 DEG C, 5 DEG C, 10 DEG C, 15 DEG C, 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C, 45 DEG C or 50 DEG C.

According to particular implementation, filter and carry out under subcritical flux.Provided hereinafter the example of the possible subcritical flux for different particle sizes and film paddy width.

For each combination of the patterned film such as shown by embodiment part hereafter and average particle size particle size, critical flux can be calculated.

According to filter method described herein, filtration can be carried out under any pressure.In some embodiments, filter and carry out between 6psi and 51psi.In other embodiments, filter and carry out under 6psi, 10psi, 15psi, 20psi, 25psi, 30psi, 35psi, 40psi, 45psi, 50psi or 51psi.

Concrete embodiment comprises the method from the component of aqueous solution filtration MW between 0.1kDa and 1000kDa.The method comprises makes the aqueous solution containing component by film as disclosed herein.In another embodiment, the method is carried out under subcritical flux.In another embodiment, subcritical flux is greater than 40Lm ^-2h ^-1.In another embodiment, critical flux can be at 40Lm ^-2h ^-1and 60Lm ^-2h ^-1between or at 60Lm ^-2h ^-1and 90Lm ^-2h ^-1between.In another embodiment, when the diameter of component has the average particle size particle size of 500nm, critical flux is greater than 60Lm ^-2h ^-1.

Concrete embodiment comprises the method from the component of aqueous solution filtration MW between 0.1kDa and 1000kDa.The method comprises makes the aqueous solution containing component by film as disclosed herein, wherein when component has under 298K 4 × 10 ^-13m ²/ s to 4 × 10 ^-9m ²during average water diffusion coefficient between/s, critical flux is 5Lm ^-2h ^-1to 90Lm ^-2h ^-1.

One embodiment further provides the method preparing patterned film.These methods comprise the use of nanoimprint lithography (NIL).NIL used can be embossing NIL or stepping-flash of light NIL.When using embossing NIL, in some embodiments, at the temperature of pressure and rising, film is applied to the rigid die comprised to be placed to the pattern on film, continues the specific time period.Then release pressure and reduce temperature.Then film is separated with mould, causes the pattern from mould to be stamped on film.In some embodiments, rigid die is made up of silicon, and in other embodiments, rigid die is made up of polymer, metal, glass, pottery, composite or its combination; Specifically, mould can be made up of very hard and heat stabilized polymer.In some embodiments, temperature is elevated to the glass transition temperature higher than film.But in specific embodiment, film need not heat so far.Being used for can between 50 DEG C and 200 DEG C to the temperature range on film by imprint patterns.In other embodiments, temperature is 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C or 200 DEG C.In some embodiments, pressure is increased with by pattern is from die marks to film.In a specific embodiment, pressure increase is to 1MPa to 10MPa.In other embodiments, pressure increase is to 1MPa, 2MPa, 3MPa, 4MPa, 5MPa, 6MPa, 7MPa, 8MPa, 9MPa or 10MPa.

In some embodiments, film and mould be exposed to rising temperature and pressure continue between 1 second and 10 minutes.In other embodiments, the temperature and pressure that film and mould are exposed to rising continues 1 second, 5 seconds, 10 seconds, 20 seconds, 30 seconds, 60 seconds, 90 seconds, 120 seconds, 150 seconds, 180 seconds, 210 seconds, 240 seconds, 270 seconds, 300 seconds, 330 seconds, 360 seconds, 390 seconds, 420 seconds, 450 seconds, 480 seconds, 510 seconds, 540 seconds, 570 seconds and 600 seconds.

In some embodiments, after pattern is stamped into film from mould, the glass transition temperature that temperature will be low to moderate lower than film.But in a specific embodiment, film can be heated to and be greater than glass transition temperature.Being used for can scope between 25 DEG C and 100 DEG C to the temperature of the reduction on film by imprint patterns.In other embodiments, temperature is 25 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C or 100 DEG C.

In another embodiment, method uses heat embossing NIL to prepare patterned film.The method comprises: provide film; Under the pressure (such as, being about 4MPa for specific material) of 3MPa to 7MPa, in rigid die, film is pressurizeed; Film is heated to above the temperature (such as, for the temperature that specific material is between 100 DEG C and 150 DEG C) of the glass transition temperature of film; Film is cooled to the temperature of the glass transition temperature lower than film (being such as the temperature of about 40 DEG C for specific material); And film is separated with mould prepares patterned film.Pressurization and heating steps are as carried out about 180 seconds.

Present invention also offers for by nanolithographic by the equipment of imprint patterns on film of the present invention.

Embodiment

The structure of embodiment 1. patterning (veining) film and physical characteristic describe

Utilize nano impression to etch (NIL) technology, commercially available milipore filter is patterned/veining.NIL is simple and reliable manufacture method, and it can form nanoscale features with low cost, comprises the feature [49-51] being less than 10nm.There is the NIL technique of two types, that is, heat embossing NIL (TE-NIL) and stepping-flash of light NIL (SFNIL).Adopt TE-NIL, polymer film higher pressure (3-7MPa) and higher than the temperature of the glass transition temperature (Tg) of polymer under by rigid die (normally Si) pressurized.After being separated with mould at the temperature being less than Tg, then produce duplicate.TE-NIL is directly used in commercial ultra-filtration film in this experiment.In all types of film, ultrafiltration (UF) film is selected, and is because it has application and the rigid structure [52,53] of wide region compared with other commercial membrane.

Ultrafiltration is pressure-driven membrane separation process, and it is for the concentrated of Polymer Solution and purifying [53].The pore diameter characteristics of milipore filter is molecular cut off (MWCO) usually, the molecular weight of the component that molecular cut off (MWCO) indicates 90% film to retain.The MWCO scope of milipore filter is between 1kDa to 1000kDa.

PW milipore filter (10kDa MWCO, polyether sulfone) from GE Infrastructure is used as commercial membrane in this study.These films are normally used for the pretreatment of process water and the post processing of ultra-pure water, and can filter high molecular weight material, colloidal substance, protein and virus.UF film used is in this study supplied to as flat-sheet material and stored dry at ambient conditions.Before nano impression, film is not carried out to the process of any type.

The nano impression of milipore filter carries out on Eitrie 3 (Obducat Inc) nano marking press.The feature of the mould applied is to have the parallel lines (834nm periodically, the ditch depth of 200nm) of space grating and comprises silicon oxide surface.Mould adopts Piranha washing lotion (sulfuric acid and hydrogen peroxide) to process before the use.Carry out Patternized technique at 120 DEG C and under the pressure of 4MPa and continue 180s.Mould is separated at 40 DEG C with duplicate.Carry out NIL usually above on the Tg of polymer, but the present invention uses the temperature (about 183 DEG C) far below the Tg of measured polyether sulfone in this experiment.The Tg of perforated membrane is determined by nanoscale thermal analyses (nano-TA).The detailed description of nano-TA technology and they are in order to determine that the application of the Tg of supported polymer can find [54] elsewhere.In the temperatures print of the Tg being close to or higher than film, the loose structure of film is caved in.When impressing at higher than arbitrary temperature of 160 DEG C, in the experiment of this group, film used becomes impermeable.But the loose structure of poly (ether sulfone) film makes do not have caving in of loose structure in the temperatures print lower than Tg.Therefore, we think, the useful temperature regime for imprint step is the scope of the Tg about 30 DEG C to 80 DEG C lower than particular polymers.In addition, for other polymer types, the pressure of 4MPa can change; Any pressure being enough to prepare imprinted pattern can be selected.

Embodiment is manufactured herein can impress over their whole surfaces with film used, or impression can be limited to the working region of filter.That is, the perimeter of film or other regions (fluid be filtered is not by these regions) do not need to be patterned, and it is commonly used to filter to be fixed in support or fixture.In addition, although directly carry out NIL to existing commercially available basal lamina material in experiment discussed herein, but it is contemplated that, patterned layer otherwise can add basement membrane to.The material of patterned layer can or can not be identical with the material of film, and patterned layer or basement membrane can by including but not limited to that the method for NIL is formed.

The AFM of original membrane and patterned film (AFM) image has been shown in Figure 1A and Figure 1B.By using the Dimension 3100VEECO AFM of yardstick (dimension) tapping-mode, utilizing silicon cantilever probe to carry out measurement AFM and measuring.Show the height image of original membrane in figure ia.Horizontal line instruction in Figure 1A and Figure 1B is by the position of scanning in order to the respective cross section profile of generation respectively shown in Fig. 1 E and Fig. 1 F, and plus sige (+) on a horizontal indicates the position indicated with vertical line in Fig. 1 E and Fig. 1 F.Original membrane has the roughness being approximately less than 10nm at first.After stamping, as shown in figure if, the average height of film becomes about 120nm.It should be noted that the cross-sectional profiles of the cross-sectional profiles of patterned film and mould used is inconsistent.Which imply that, owing to using the lower temperature different from conventional NIL, therefore the VISCOUS FLOW of material can not be realized.Obviously, imprint process becomes pressure and occupies an leading position, and causes the pattern height declined.We have also investigated the cross section shapes adopting film before and after field emission scanning electron microscope (FE-SEM) (Zeiss, Supra 60) impression.At low-down temperature (-20 DEG C), use the cross section of microtome knife cutting film.The cross-section SEM images of original membrane has been shown in Fig. 1 D.SEM image shows, and film has dissymmetrical structure, and it has at the top layer on top and non-woven polyester support (PES) layer.Fig. 1 C illustrates the cross sectional image of patterned film.SEM image shows, and the dissymmetrical structure in PES is lost due to high compression, and PES layer is compressed.

In view of the above results, the contemplated method preparing filter membrane comprises: use NIL, film generates nanoscale features.Filter membrane comprises: (1) has the basement membrane of first surface and the second surface relative with first surface, (2) pattern formed by the material compatible with basement membrane, the working region of this pattern covers first surface, pattern formation has size and is no more than the periodicity of 1 micron and the feature of amplitude.This pattern can by impression basement membrane or by patterning materials is added to basement membrane to be formed.The material that is solvable and/or that suspend that pattern decreases that surface gathers and the mass transfer of particle from solution to film, simultaneously solution is by film, this with the surperficial material that is solvable and/or that suspend that gathers and particle from solution to not having the mass transfer of figuratum basement membrane contrary.

The use of embodiment 2. patterned film in filtration

After morphological research, carry out filtration experiment to characterize mass transfer and the contamination characteristics of patterned film.Carry out in the laboratory scale hyperfiltration equipment 200 that all filtration experiments are shown in fig. 2.This equipment is the system of unconventional lateral flow type, the charging of wherein flowing out from charging spout 220 is by 1/4 " then pipe 225 enter the pipe 240 (1/8 inch) of minor diameter by decelerator 235; then enter module 245; in module 245; center (being sightless in module 245) of film coupongs is impacted in charging; radially outwards and upwards flow to be collected retentate side by large diameter pipe 225 (1/4 inch) along both sides, it is common annular that large diameter pipe 225 is arranged to for charging.Substantially be tangential by the character of the stream on surface and radially outward.Feed suspension is maintained in the charging spout 220 be made up of stainless steel.Agitator is used, to suppress any deposition with rotating speed constant all the time in charging spout 220.Film has the effective film area of 1.93cm2.At experimental session, the high pressure nitrogen in groove 210 is used to provide pressure by pipe 215 pairs of grooves 220.The pressure in pipe 225 and pipe 240 monitored by pressure gauge scale 230 and 250.All filtration experiments carry out under room temperature (21 DEG C).Permeation flux adopts the electronics level (PI-225DA, Denver Instrument, the U.S.) being connected to computer to measure.Utilize the flow regulator 255 being discharged to unlimited container 260, by keeping constant retentate volume flow velocity, the shear rate on whole film surface keeps constant in whole experiment.Peristaltic pump 270 (I/P easily assembling, Masterflex, the U.S.) is used to retentate again to circulate with the volumetric rate of 60mL/min the feed suspension returning and enter groove 220 from container 260.

The contamination characteristics of film adopts the conceptual analysis of " critical flux ".Critical flux J _critbe called as the permeation flux that the membranous system polluted does not occur in this article.Ideally, for clean system, the transmembrane pressure (TMP) of flux all the time with applied of film is proportional.When flux exceedes the critical value for solution/suspension, irreversible deposit and/or pollution start, and flux starts to depart from the linear relationship with TMP.Field etc. introduce the concept of critical flux first in nineteen ninety-five, and its constant flux being devoted to yeast cells filters and MF (micro-filtration).Critical flux is defined by: lower than this flux, TMP does not increase in time [55].Howell etc. also confirm the existence of critical flux and subcritical flux, and wherein, for specific flux, TMP keeps constant [56] in time.Researcher proposed dissimilar experiment to calculate/measure critical flux.By utilizing flux stepping method, Bacchin etc., Kwon etc. and other researchers measure for silica suspension in order to maintain the given necessary transmembrane pressure of transmembranal penetration flux [57-59].When TMP can not obtain stable state in time and flux-TMP relation becomes non-linear, multiple researcher it is also proposed pressure stepping method to find out critical flux [60,61].

In this experiment, pressure stepping method adopts colloidal suspension liquid, and it has been widely used to characterize critical flux.Normally well-known at fouling membrane theoretical background behind for colloidal suspension liquid, the wherein balance [62,63] of critical flux normally pellet-pellet or particle-film repulsive force and infiltration drag.When being greater than the set-point of flux, when repulsive force permeated drag overcome time, deposit is formed on the surface of the film and produces the other resistance of osmotic fluid through film." AngstromSphere " silica dioxide granule (Fiber Optic Center, MA, the U.S.) of different size is with in this experiment to prepare colloidal suspension liquid.These perfect spherical silica particles are unbodied, non-hole and containing a large amount of silicone hydroxyl (Si-OH) groups so that diffusion in water.By adopting the silicon dioxide nanosphere of a FL-70 surfactant-dispersed variable quantity and vigorous stirring more than 12 hours, prepare colloidal suspension liquid.Before filtration experiment, utilize ultrasonic generator minimum lasting 60 minutes, solution is carried out ultrasonic process and 15 minutes can be continued by cool to room temperature.

Fig. 3 illustrates the result of the critical flux experiment adopting colloidal suspension liquid and DI water to carry out.Fig. 3 illustrates the Line Chart according to the relation between the transmembrane pressure applied for original membrane and patterned film of embodiment and flux, its be depicted as transmembrane pressure with for water with use 5gL ^-1the filtration flux of the colloidal suspension liquid of the latex particle of concentration, wherein, crossing current volume flow rate 1.5mL s in a device ^-1.During water filtration and silica dioxide granule are filtered, black (solid) symbol represents the permeability for original membrane, and open symbols represents the permeability of patterned film.Square symbols represents the permeability of the pure water for two kinds of films.For the water permeation rate of original membrane and patterned film also by linear fit, represent respectively by solid line and dotted line.Triangle, circle and star symbol are corresponding to the permeability of colloidal suspension liquid corresponding respectively to 250nm, 500nm and 1000nm latex particle.

For each filtration experiment, first deionization (DI) water changed pressure by infiltration as charging simultaneously, then measures PWP J ₀.For each sample, DI water filters 20 minutes under constant pressure.Pressure linearly increases to 50psi from 6psi.As expected, the permeation flux of pure water linearly increases along with transmembrane pressure.The water permeation rate of original membrane is represented by dark square, and the water permeation rate of patterned film is represented by open squares.

Although high compression impresses, but the PWP of patterned film finds the permeability being similar to original membrane.From about 12% less permeability at low pressures, PWP reaches original value at a higher pressure.Compressing hole swelling of patterned film may be the reason of this result at elevated pressures.For the water permeation rate matching and representing respectively by solid line and dotted line linearly of original membrane and patterned film.Overall water permeation rate is gone out and by it shown in following table 2 from this Fitting Calculation.

Depict the flux of original membrane for colloidal suspension liquid and patterned film in figure 3 together.Black (solid) triangle, circle and star symbol are corresponding to the permeability of original membrane of colloidal suspension liquid being respectively used to 250nm, 500nm and 1000nm latex particle, and hollow triangle, hollow circle and hollow star symbol represent the permeability of the original membrane of the colloidal suspension liquid for 250nm, 500nm and 1000nm latex particle.The point place starting departs from linear water permeation rate line in colloid osmotic rate starts to pollute.

All suspension illustrates the critical flux of strong form, because they do not start to pollute at first.The critical flux measurement of strong form is particular importance, because it points out that absorption is negligible.This means, filter performance and well make pollutional condition depend on the interaction of latex/silica-film.For all experiments, critical flux value and corresponding pressure are listed in table 2.When having the original membrane of 250nm particle, ~ 33L m ^-2h ^-1critical flux when being in 15psi, pollute and start.For identical particle size, ~ 47L m ^-2h ^-1critical flux when being in 22.5psi, in patterned film, there is critical flux.For the colloidal suspension liquid utilized prepared by 500 nanometer silicon dioxide particles, ~ 51L m ^-2h ^-1critical flux when being in 15psi, original membrane starts to pollute.For the particle of same size, ~ 74L m ^-2h ^-1critical flux when being in 27.5psi, patterned film starts to pollute.For the colloidal suspension liquid of 1000nm particle, ~ 59L m ^-2h ^-1critical flux when being in 20psi, original membrane starts to pollute.For patterned film, ~ 70L m ^-2h ^-1critical flux when being in 25psi, pollute.

For original membrane, 250nm particle provides minimum critical flux and 1000nm particle produces higher critical flux.This trend observed finds consistent with the experiment of multiple researcher.This effect is ascribed to associating of the different critical flux mechanism of diffusion (higher for less particle) and surface interaction (higher for larger particle) by Harmant with Aimar.But for the particle of all sizes, the critical flux in patterned film is higher than the critical flux in original membrane.The highest critical flux finds when the particle of 500nm, and wherein, before pollution, flux increases 45%.The trend that less particle size has lower critical flux is consistent with the result of original membrane.But, for the critical flux of 500nm particle higher than the critical flux for 1000nm particle.This shows the hydrodynamic effect that size is relevant, and this effect is mainly used in the particle of 500 nanometers.It should be noted that the paddy produced by imprint process is 400nm.Although do not observe the every other effect being similar to absorption and reversible pollution in this experiment, but whole polluting effect can be the fluid dynamic result near film surface.The 500nm particle adopted together with 400nm paddy can produce best hydrodynamic effect, and wherein, this particle can not occupy whole paddy.For 1000nm particle, 400nm paddy can be very little, and therefore pellet-pellet interacts and may be greater than the interaction of particle-paddy.

In order to compare contamination phenomenon all sidedly, pollute resistance R _falso calculate from filtering data.In theory, for pure water, flux, relation between driving force and resistance can be represented by Darcy's law:

$J=\frac{\mathrm{\Δp}}{\mathrm{\μ}\·R}$

Wherein, J is flux, and Δ P is transmembrane pressure, and μ is the viscosity of percolating solution, and R is resistance.After pollution, equation can become:

$J=\frac{\mathrm{\Δp}-\mathrm{\π}}{\mathrm{\μ}\·(R_m+R_f)}$

Wherein, R _mbe membrane resistance, it calculates from PWP, R _fbe pollute resistance, other resistance provides pollution layer, and π is osmotic pressure, and it can be determined by concentration polarization.In these experiments, the effect of the osmotic pressure caused by concentration polarization to flux is left in the basket, and this is the low infiltration coefficient due to silica sphere.

All experiment pollution resistances under a constant that pollutes are calculated and depicted in Fig. 4 and polluted the Line Chart that resistance is the experimental data of the time correlation for original membrane and patterned film and colloidal suspension liquid illustrated according to embodiment to TMP, Fig. 4.Black (solid) symbol represents the pollution resistance of the silica dioxide granule for sizes all in original membrane, and open symbols represents the pollution resistance for patterned film.Right angled triangle, rhombus and pentagon symbol represent the pollution resistance of the colloidal suspension liquid being respectively used to 250nm, 500nm and 1000nm latex particle.For all colloidal suspension liquids, initial pollution Resistance Value is lower and be constant.To pollute and critical flux point easily can be identified as the point that pollution resistance starts along with pressure increase.As desired by from the TMP-flux pattern in Fig. 3, start after the pollution resistance for pollution resistance original membrane under respective conditions of patterned film.

500nm colloidal suspension liquid for patterned film starts to pollute the film that will be later than any other.Although this result and TMP-flux relationship consistency, but Fig. 4 provides the other information about accumulated pollution.Pollute resistance instruction pollution layer how to set up on the surface of the film.For the growth rate of the pollution resistance of patterned film also lower than the growth rate of the pollution resistance for original membrane.Except critical flux value, this instruction, compared with original membrane, is not only polluted and is grown on patterned film in the later stage, and it is also lower in critical flux situation to pollute speed.

When film operates in the pressure lower than the relevant pressure of critical flux, it may be defined as and operates in " subcritical flux " district.Then, when under the pressure that film operates in higher than critical flux pressure, the Chao – critical flux of its “ " operate in district.In theory, when film operates in close-to-critical range, particle-film repulsive force and/or diffuse in reverse direction are subsequently higher than infiltration drag.In this zone, membrane flux remains unchanged in time.

In order to check and examine from polluting the critical flux value of testing and obtaining, colloidal solution is adopted also to carry out the research with time correlation.The colloidal solution of 500nm silica dioxide granule is used for the research of time correlation.Fig. 5 A and Fig. 5 B illustrate utilize respectively patterned film and original membrane to filter colloidal suspension liquid with the research of time correlation.For two kinds of films, select two pressure.Because the critical flux for patterned film starts from 27.5psi place, so 22.5psi is selected as the point operated in subcritical flux zone, and 32.5psi is selected as the point operated in overcritical flux zone.For each pressure, filter and carry out 100 minutes and flux carried out record every 2 minutes.

Fig. 5 A be illustrate according to embodiment utilize the colloidal suspension liquid of patterned film with the Line Chart of the experimental data of time correlation.In fig. 5, this illustrate according to time and flux draw utilize patterned film under a constant with the experimental result of time correlation.The research that black diamonds symbol table operates under being shown in 22.5psi and open diamond symbols represent the research carried out under 32.5psi.From these research, obviously, 22.5psi remains in close-to-critical range, and this is because flux keeps very constant within the time of 100 minutes, and for the pressure of 32.5psi, in supercritical region, film from initial just pollute.This experiment shows, critical flux occurs between 32.5psi and 22.5psi clearly.

The identical experiment adopting same approach is repeated to original membrane.Fig. 5 B be illustrate according to embodiment utilize the colloidal suspension liquid of original membrane with the Line Chart of the experimental data of time correlation.In figure 5b, this illustrate according to time and flux draw under a constant for original membrane with the experimental result of time correlation.Because when original membrane, 500nm colloidal solution critical flux be found to be 15psi, 10psi is selected as the pressure for close-to-critical range and 20psi is selected for overcritical flux.Original membrane also finds consistent result.For the filtration run at 10 psi, flux keeps constant along with the time, and for 20psi, original membrane is starting to pollute at first.

The feature of the film that embodiment 3. is polluted

After overcritical flux place filters, two kinds of polluted membranes (patterning with original) utilize SEM to characterize.Before microscopic analysis, then film adopts 4.7nm layer gold sputtering coating for dry 24 hours at room temperature and pressure.Fig. 6 A is the schematic diagram that NIL-patterned film direction is shown, and Fig. 6 B illustrates the schematic diagram selected for nine parts of the NIL-patterned film of sem analysis, and patterning on the direction illustrated in fig. 6, wherein, arrow instruction is relative to the direction of the tangential runoff of pattern.

As depicted in figure 6b, because the existence of pattern, therefore the different piece of patterned film flows to over their surface relative to pattern direction and has different orientations.Exemplarily, the pattern in the part 4 at the top place of Fig. 6 B has 90 ° of orientations relative to the flow direction, and part 2 be parallel to flow to and directed.

The patterned film polluted is cut into 9 parts as illustrated in figure 6b.The upper left-hand image of Fig. 6 B represents the orientation of pattern on film, and upper right side image illustrates how to select part for microscopic analysis.For each sample, take five images on the whole surface with the distribution of detected silica particle.Utilize ImageJ software (National Institute of Health, the U.S.), according to mean value and the surface coverage of SEM image evaluation particle.Subsequently, the original membrane of pollution is also divided into 9 parts and adopts SEM to characterize.It should be noted that original membrane does not have any difference, this is because its surface has uniform random roughness (see Figure 1A and Fig. 1 E) in its surface in the flow direction with picture on surface.As for Patterned Sample complete, pollute primary sample whole surface on, relative to feed jet at same position place, take nine images, use ImageJ carry out evaluation surface coverage.Fig. 7 A and Fig. 7 B illustrates the deposition distribution of particle on polluted membrane.Fig. 7 A illustrates the representative image for patterned film, and Fig. 7 B illustrates the representative image for original membrane.The surface coverage analyzed by ImageJ for all parts is reported in following table 3.

Overall deposition (pollution) (19.4%) for patterned film finds much smaller than deposition (pollution) (66.2%) in original membrane.Which illustrate the lower growth rate of the pollution resistance of patterned film.Deposition a small amount of silica on the surface of the film can indicate accumulated cake to be prevented from by infiltration drag higher during filtering technique.For this reason, particle can keep unstable, and this causes deposition less on the surface of the film.Surprisingly, for the part of the orientation perpendicular to the flow direction, find even less deposition (surface coverage of 2.2%).Flowing to directed part for being parallel to, finding the highest deposition (surface coverage of 57.36%).Apparently, surface coverage illustrates the flow direction close association on pattern.In theory, on pattern, the stream of vertical orientation will produce the turbulent flow larger than other flowing positionings.Subsequently, on pattern, the stream of parallel orientation will not produce any turbulent flow.The effect of turbulent flow is obvious herein, and it also seems to affect overall penetration drag.When the surface coverage of the part of patterned film compares with the surface coverage of the part of original membrane, show clearer image.Different from patterned film, original membrane does not have any unique flowing positioning in its surface, and it is random for being therefore deposited in all parts.In addition, the deposition of the part that the great majority that this deposition finds to be greater than patterned film pollute.

Find out significantly from experiment, patterned film can than original membrane pollution abatement better.(and orientation) surface roughness increased is apparent that the unique difference between these films.Possibly, the surface roughness improved in patterned film can increase pellet-pellet and interact or particle-exclusion power (causing the pollution abatement thus of larger diffuse in reverse direction).The roughness increased in film surface also should increase the turbulent flow of film surface.But the different size due to dirt illustrates different contamination characteristics, therefore hydrodynamics is not the sole cause after the pollution resistance improved.Particle-surface interaction also should play a significant role.When particle size is just slightly larger than paddy width, find to improve alleviating of pollution larger.Finally, most probable ground, the hydrodynamics of improvement and the combination interpretation of the higher particle-exclusion power pollution resistance improved in patterned film.

Utilize NIL technology, commercial membrane creates pattern.This demonstrates the cost efficient mode in order to the existing commercial membrane of veining, and it can be used in batch production by volume to volume NIL.This is the reported first utilizing the direct veining filter membrane of this technology.Different from the NIL technique of routine, low temperature impression is practical for veining perforated membrane.But pattern height realized in this process caves in about 45% from mould.In imprint process, loose structure supports that some change really, but the PWP for patterned film finds not considerably beyond original membrane water permeation rate.By using striated pattern patterned film, when comparing with original membrane, polluting and also alleviating.Use the texture of this simple form, achieve critical flux and increase about 45%.What is interesting is, when paddy/groove be slightly less than dirt measure time, achieve best pollution and alleviate.When Brennan etc. utilizes the dimethione of veining (PDMS) to study the dirt of different size, Brennan etc. also states similar conclusion [39].According to these results, can think, adopt the embodiment of periodicity and/or the feature of amplitude in the scope of 60% to 100% of average particle size particle size the pollution provided to be alleviated.

Patterned film not only increases critical flux, and alleviates the deposition/pollution rate after pollution starts to occur.The microscopic analysis of polluted membrane also shows, and the deposition of the deposition rate original membrane on patterned film is little by about 70%, in addition, pollution deposit discovery and patterned surface flows to close association.For flowing the region of orientation perpendicular to surface, find that the pollution deposit ratio in patterned film is medium and small by 97% in original membrane.

In view of the above results, can comprise from the method for solution filter component: make the solution comprising component pass through film, this film comprises: (1) has the basement membrane of first surface and the second surface relative with first surface, and basement membrane is formed by the material compatible with solution; (2) pattern formed by the material compatible with solution with basement membrane, the working region of this pattern covers first surface, pattern formation has size and is no more than the periodicity of 1 micron and the feature of amplitude.This pattern or can add additional materials to basement membrane and be formed by impression basement membrane.The material that is solvable and/or that suspend that pattern decreases that surface gathers and the mass transfer of particle from solution to film, simultaneously solution is by film, this with the surperficial material that is solvable and/or that suspend that gathers and particle from solution to not having the mass transfer of figuratum basement membrane contrary.The method can comprise one of the flow and pressure of adjustment solution to provide the subcritical flux of the solution by film.By using the solution of the first consumption to determine the flow or pressure that correspond to critical flux, provide the pressure of subcritical flux and/or flow can be determined by the pollution characterizing the first film, this first film comprises identical basement membrane and identical pattern.Then, when solution is by film for filtering, the solution of the second consumption can by comprising the second film of identical basement membrane and pattern, utilizes information from characterisation step to adjust one of flow and pressure to provide subcritical flux.

The NIL-patterning effects of embodiment 4. in protein ultrafiltration

Utilize and the identical experimental system for describing in the previous embodiment of colloidal particles, test, to determine the absorption by being reduced in the solute polymer (protein) on surface, the turbulent flow (local mixing) passing through increase local and/or the physical chemistry attraction be reduced between solute and film surface, whether pattern can strengthen the strainability of ultrafiltration (UF) film.

This preliminary research presents the result of the single patterned strategy on the commercially available polyether sulfone (PES) of the specified MWCO with 10kg/mol.This result illustrates as follows:

Create pattern.

Pattern comprises the line-spacing grating with centre-to-centre spacing 833nm, line-spacing ratio=1, highly: 40 ~ 100nm.

Pattern does not adversely affect the quality factor of the baseline of film.

Pattern reduces model proteins absorption from the teeth outwards really.

Pattern reduces absorption, increases the time m-efficiency average of film.

In a word, these results have economic worth in various current industrial application.

Bovine serum albumin(BSA) (BSA) is the pattern dirt of generally acknowledging used in bio-separation and membrane for water treatment research.How this experiment measuring cleaning film for the resistance of pure water stream, the resistance for the stream of the solution containing BSA, and easily removes the BSA of any deposition.Therefore, determine BSA and be attached to the amount on surface and the intensity of its attachment.

Employ the film of two types in this study: original (non-NIL patterning) and NIL-patterning, PES film.This solution comprises the BSA in phosphate buffer (PBS) of 1g/L.

First, deionization (DI) water filtration membrane under constant transmembrane pressure, at every cm ²membrane area collect 10mL penetrant during, determine permeability.Then, under a constant filtration buffer solution to determine collecting other 10mL/cm ²penetrant during permeability.BSA is added to feedstock solution and is filtered during the penetrant collecting other 20mL.BSA charging adopts buffer solution to replace, again Measurement sensibility state buffering permeability.Then buffering charging replaces with DI water, and whole groove (cell) is cleaned to remove deposit.Finally, rinse solution buffer solution replaces, and again measures permeability.

Result is summarized in Fig. 8 A, Fig. 8 B, Fig. 9 and Figure 10 A to Figure 10 D.Fig. 8 A and Fig. 8 B illustrates the productive rate of film.For three kinds of solution (DI water, buffer solution and BSA+ buffer solution), the productive rate (value on vertical pivot) of film is different and changes in time, this is because:

1. film compresses due to institute's applied pressure;

2. the viscosity of solution is different;

3. deposition of solute is on film surface or in its hole.

Fig. 8 A illustrates the productivity ratio of non-NIL-patterned film (namely original).Above-mentioned experimental procedure (in the method) is the region of being separated by arrow.Step 1 performs twice under two kinds of different pressure.All measurement scheme illustrate in order.The region marked corresponds to measurement scheme, as follows: region 802 illustrates the permeability of DI water under 30PSI.Region 804 illustrates the permeability of DI water under 40PSI.Region 806 illustrates the permeability of independent PBS under 40PSI.Region 808 illustrates the permeability of PBS+BSA under 40PSI.Region 810 illustrates the permeability of the independent PBS after the condition of region 808.Region 812 illustrates the permeability of independent PBS after the cleaning process.

Fig. 8 B illustrates the productivity ratio of NIL-patterned film (it should be noted that vertical axis is different from Fig. 8 A).Adopt the scheme identical with non-NIL (original) film, and experimental procedure (in the method) is as described above the region split by arrow.Step 1 is carried out twice at two different pressures.All measurement scheme are shown in order.The region marked corresponds to measurement scheme, as follows: region 822 illustrates the permeability of DI water under 30PSI.Region 824 illustrates the permeability of DI water under 40PSI.Region 826 illustrates the permeability of independent PBS under 40PSI.Region 828 illustrates the permeability of PBS+BSA under 40PSI.Region 830 illustrates the permeability of the independent PBS after the condition of region 808.Region 832 illustrates the permeability of independent PBS after the cleaning process.

Finding out from Fig. 8 A and the obvious of Fig. 8 B, is 2.5 times (0.3g/min and 0.12g/min) of the PBS flux of non-patterned (original) film after the washing for PBS (buffer solution) flux of NIL patterned film.

Fig. 9 illustrates, result is repeatably and when adopting identical scheme, NIL (patterning) film demonstrates statistically significantly advantage than non-NIL (original) film in productivity ratio.Should note, pure water or buffer solution permeability exist little loss (we notice identical result in particle filtering embodiment), but during employing foul solution filters and after filtering, NIL-patterned film provides relative to non-NIL patterning (original) film and significantly improves.

In addition, test protein absorption on the surface of the film through the following steps:

~ 80mm ²the filter block of pollution cut and in ice bath, carry out ultrasonic process continue 60 minutes

As shown in Table 4 below, the BSA of desorption is in the solution measured by UV-Vis (@280nm).

Amount is in the solution (with mg/cm ²represent) mean that more greatly the amount of adsorbing on film after experiment is larger.

SEM is also used for the deposition on visualization surfaces.The surface (Figure 10 C and Figure 10 D) of NIL-patterned film seems cleaner than the surface (Figure 10 A and Figure 10 B) of non-NIL patterning (original) film.

Figure 11 A schematically shows the impressing mould 1150 of locating relative to basement membrane 1100.Film 1100 is compatible with permeable relative to the solvent for filtering.Mould 1150 is rigidity and is such as made up of silicon, polymer, metal, glass, pottery, composite or its combination.Mould 1150 is shaped as the negative replica of the nano-scale patterns treating to prepare in film.

As discussed above, mould 1150 can be used for imprint patterns to enter basement membrane 1100, to prepare patterning filter membrane 1110 as shown in Figure 11 B.Film 1110 is included in the pattern (only characteristic features 1120 is listed in Figure 11 B, the object for clearly demonstrating) formed by feature 1120 in the working region 1130 of film 1110.Feature 1120 can not to scale (NTS) illustrate, specifically, feature 1120 relative to basement membrane 1100 size, periodically, aspect ratio and highly can along with as discussed above for needed for particular filter scheme and change.

Figure 12 schematically shows the filter membrane 1200 formed by the pattern 1220 adding basement membrane 1210 to.Basement membrane 1210 and pattern 1220 are both compatible with permeable about the solvent for filtering.Figure 12 illustrates the pattern 1220 only in the working region 1230 of film 1200, but pattern 1220 can in the outside of working region 1230 on whole basement membrane 1210 upper part ground or fully extend in other embodiments.

Therefore the bibliography comprising patent and publication quoted herein is incorporated to herein by the mode quoted in full.

The combination of feature

Although emphasis adopts particular implementation to describe the present invention, but those of ordinary skill in the art to be it is evident that, the modification of embodiment can be used, its objective is, the present invention can with from specifically describe different modes herein to implement.Such as, instruction herein can as in any combination apply conceive, no matter and whether clear and definite open like this.Therefore, the present invention includes all modification included in the spirit and scope of the present invention limited by appended claim.Specifically, it should be noted that the particular combination of following characteristics is possible:

A) in embodiments, film for fluid conveying comprises: the basement membrane with first surface and the second surface relative with first surface, with the pattern formed by the material compatible with basement membrane, the working region of this pattern covers first surface, pattern formation has size and is no more than the periodicity of 1 micron and the feature of amplitude.

B) after manufacturing film in the mode of applicable commercial use, the film of item (a) can be formed by nanolithographic.

C) arbitrary film of item (a) or item (b) can comprise: etch formed pattern by nanometer alternatively at least one surface.When fluid is transmitted through film, compare from fluid to the mass transfer of the working region not having figuratum basement membrane with particle with the material that is solvable and/or that suspend that surface is gathered, the material that is solvable and/or that suspend that surface can be gathered by the periodicity of pattern and/or amplitude and the mass transfer of particle from fluid to working region are reduced by least 10% effectively.

D) mass transfer of arbitrary film of item (a), item (b) or item (c) material that is solvable and/or that suspend that surface can be gathered and particle reduces 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or 100%.

E) item (a) to arbitrary film of item (d) can be used for filter liquide or gas.

F) arbitrary film of item (a) to (e) can be used for filtering polar solvent, is especially selected from the polar solvent of following material: carrene, oxolane, ethyl acetate, acetone, dimethyl formamide, acetonitrile, methyl-sulfoxide, propene carbonate, formic acid, n-butanol, isopropyl alcohol, normal propyl alcohol, ethanol, methyl alcohol, acetic acid and water.

G) arbitrary film of item (a) to (e) can be used for filtering non-polar solven, especially the non-polar solven of following material is selected from: pentane, pentamethylene, hexane, cyclohexane, benzene, toluene, Isosorbide-5-Nitrae-dioxane, chloroform and diethyl ether.

H) the arbitrary film in item (a) to (g) can be filter membrane, milipore filter, nanofiltration membrane, microfiltration membranes or reverse osmosis membrane.

I) the arbitrary film in item (a) to (h) can comprise following material: polyether sulfone, polyacrylonitrile, polyvinylidene, regenerated cellulose, cellulose acetate, polysulfones, polypropylene, polyether sulphone, Kynoar, polyvinyl chloride, polyketone, polyether-ketone, polytetrafluoroethylene (PTFE), polyimides and polyamide, polypiperazine-amide, polyamide, polyethylene, polypropylene, polysulfones, polyether sulfone, polyvinylidene fluoride, nylon, mixed cellulose ester, polycarbonate, polystyrene, polyvinyl chloride or comprise glassy state or the rubbery feel polymer of dimethione.

J) the arbitrary film in item (a) to (i) can be included in raised or sunken part film being formed shape.This shape can comprise jut, parallel lines, intersecting lens, concentric line, crestal line, paddy, passage, on one or both sides by paddy around jut, hills, bar, mountain peak, pin, pin and/or knob.Parallel lines also can comprise the other line crossing with parallel lines, this other line can one or more angle places between about 0.01 ° and 90 ° crossing with parallel lines.

K) the arbitrary film in item (a) to (j) can comprise the shape of arranging on film with periodicity between 10nm and 1500nm, between 400nm and 1000nm or between 600nm and 800nm and/or amplitude.When their the widest some place measurements, this shape can have these sizes.At the average height place of film, paddy or passage can have between 200nm and 800nm, between 300nm and 600nm or the width of about 400nm.

L) can comprise by the arbitrary film item (a) to (k) from the method for aqueous solution filter component, the aqueous solution comprising component is passed through.

M) method of item (l) can comprise the component of filtering and having molecular weight between 0.1kDa and 1000kDa and/or can perform at subcritical flux place.

N) in the method for item (m), when component is when diametrically having the average particle size particle size of 250nm, critical flux can be greater than 40Lm ^-2h ^-1, or critical flux can at 40Lm ^-2h ^-1and 60Lm ^-2h ^-1between, especially at 60Lm ^-2h ^-1and 90Lm ^-2h ^-1between, and when component is when diametrically having the average particle size particle size of 500nm, critical flux can be greater than 60Lm ^-2h ^-1.

O) in the method for item (m) and/or item (n), at 4x 10 under component has 298K ^-13m ²/ s to 4 × 10 ^-9m ²during average water diffusion coefficient between/s, critical flux can at 5Lm ^-2h ^-1to 90Lm ^-2h ^-1between.

P) a kind of preparation (a) can comprise nanometer embossing (NIL) to the method for the film in item (k).NIL can be heat embossing NIL or stepping-flash of light NIL.Heat embossing NIL can comprise: provide film; Under the pressure of about 3MPa to 7MPa, in rigid die, film is pressurizeed; By film heating to make impression; Film is cooled; Then film is separated with mould.Heating film can comprise the temperature be elevated to by film between 100 DEG C and 150 DEG C.Film cooling can be comprised temperature film being reduced to the glass transition temperature lower than film, about 40 DEG C alternatively.

Q) in the method for item (p), rigid die can be made up of one or more in silicon, polymer, metal, glass, pottery or composite.

The working region that r) can be included in polymer film for the preparation of the method for film of fluid conveying forms nano-scale patterns.Formation can comprise the working region utilizing rigid die pressure to be applied to polymer film, and this rigid die is configured as the negative replica of nano-scale patterns, and pressure is enough to generate nano-scale patterns in the polymer; Film is heated to lower than polymer Tg about 30 DEG C to the temperature in the scope of 80 DEG C; Film cooling is kept this pressure simultaneously; And film is separated with mould.

S) in the method for item (p), rigid die can comprise in silicon, polymer, metal, glass, pottery or composite one or more.

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Claims (19)

1., for a film for fluid conveying, comprising:

Basement membrane, described basement membrane has first surface and the second surface relative with described first surface, and

The pattern be made up of the material compatible with described basement membrane, the working region of first surface described in described pattern covers, described pattern formation has size and is no more than the periodicity of 1 micron and the feature of amplitude.

2. film as claimed in claim 1, described pattern is formed by nanolithographic at least one in described first surface and described second surface, wherein, when fluid is transmitted through described film, compare from described fluid to the mass transfer of the working region not having the described basement membrane of described pattern with particle with the material that is solvable and/or that suspend that surface is gathered, the material that is solvable and/or that suspend that surface is gathered by the described periodicity of described pattern and amplitude and particle decrease at least 10% from described fluid to the mass transfer of described working region.

3. film as claimed in claim 1, wherein, described basement membrane and described pattern and polar solvent are compatible, and described polar solvent is selected from carrene, oxolane, ethyl acetate, acetone, dimethyl formamide, acetonitrile, methyl-sulfoxide, propene carbonate, formic acid, n-butanol, isopropyl alcohol, normal propyl alcohol, ethanol, methyl alcohol, acetic acid and water.

4. film as claimed in claim 1, wherein, described basement membrane and described pattern and non-polar solven are compatible, and described non-polar solven is selected from pentane, pentamethylene, hexane, cyclohexane, benzene, toluene, Isosorbide-5-Nitrae-dioxane, chloroform and diethyl ether.

5. film as claimed in claim 1, wherein:

Described film is milipore filter, and

At least one in described basement membrane and described pattern comprises the material being selected from following material: polyether sulfone, polyacrylonitrile, polyvinylidene, regenerated cellulose, cellulose acetate, polysulfones, polypropylene, polyether sulphone, Kynoar, polyvinyl chloride, polyketone, polyether-ketone, polytetrafluoroethylene (PTFE), polyimides and polyamide.

6. film as claimed in claim 1, wherein:

Described film is nanofiltration membrane, and

At least one in described basement membrane and described pattern comprises the material being selected from following material: cellulose acetate, polypiperazine-amide, polyamide, polyethylene, polypropylene, polysulfones, polyether sulfone, polytetrafluoroethylene (PTFE), polyvinylidene fluoride, polyimides and/or polyacrylonitrile.

7. film as claimed in claim 1, wherein:

Described film is microfiltration membranes, and

At least one in described basement membrane and described pattern comprises the material being selected from following material: nylon, mixed cellulose ester, regenerated cellulose, cellulose acetate, polycarbonate, polytetrafluoroethylene (PTFE), polypropylene, polystyrene, polyvinyl chloride, polysulfones, polyether sulfone and polyethylene.

8. film as claimed in claim 1, wherein:

Described film is reverse osmosis membrane, and

At least one in described basement membrane and described pattern comprises the material being selected from following material: cellulosic acetate, polypiperazine-amide and polyamide.

9. film as claimed in claim 1, wherein:

Described basement membrane and described pattern and gas are compatible, and

At least one in described basement membrane and described pattern comprises dimethyl silicone polymer.

10. film as claimed in claim 1, described pattern comprises and forms the bossing of shape or sunk part, and it is one or more that described shape is included in crestal line on film, paddy, passage, hills, bar, mountain peak, pin, pin, knob, parallel lines, intersecting lens and concentric line.

11. films as claimed in claim 1, described pattern comprises layout jut on the membrane, and the periodicity of described jut is between 10nm and 2000nm.

12. films as claimed in claim 11, when measuring at the widest some place of described jut, the width of described jut is between 300nm and 500nm.

13. films as claimed in claim 1, wherein:

Described pattern comprise in parallel lines, intersecting lens and/or concentric line one or more, each in described parallel lines, intersecting lens and/or concentric line formed on one or both sides by paddy around jut; With

The peak of described parallel lines, intersecting lens and/or concentric line to the height of paddy between 100nm and 300nm.

The method of 14. 1 kinds of filter component from solution, comprising:

To comprise the described solution of described component by film, described film comprises:

Basement membrane, described basement membrane has first surface and the second surface relative with described first surface, and described basement membrane comprises the material compatible with described solution, and

Comprise the pattern of the material compatible with described solution with described basement membrane, the working region of first surface described in described pattern covers, described pattern formation has size and is no more than the periodicity of 1 micron and the feature of amplitude;

Wherein, the material that is solvable and/or that suspend gathered with described surface is contrary to the mass transfer of the basement membrane not having described pattern from described solution with particle, the material that is solvable and/or that suspend that described pattern decreases that surface gathers and particle are from described solution to the mass transfer of described film, and described solution is by described film simultaneously.

15. methods as claimed in claim 14, wherein, described component has the molecular weight between 0.1kDa and 1000kDa.

16. methods as claimed in claim 14, wherein, are comprised by described solution: adjust one in the flow of described solution and pressure to provide described solution by the subcritical flux of described film.

17. 1 kinds, for the preparation of the method for the film of fluid conveying, comprising:

The working region of polymer film forms nano-scale patterns.

18. as claimed in claim 17 for the preparation of the method for the film of fluid conveying, and wherein, formation comprises:

Utilize rigid mould pressure to be applied to the described working region of described polymer film, described rigid mould is shaped to the negative replica of described nano-scale patterns, and described pressure is enough to prepare described nano-scale patterns in the polymer;

Described film is heated at the Tg lower than described polymer about 30 DEG C to the temperature in the scope of 80 DEG C;

Described film is cooled, keeps described pressure simultaneously; With

Described film is separated with described mould.

19. methods as claimed in claim 18, wherein, described rigid die comprise in silicon, polymer, metal, glass, pottery or composite one or more.